EP2470372B1 - Verfahren zur herstellung eines flüssigkeitsausstosskopfs - Google Patents

Verfahren zur herstellung eines flüssigkeitsausstosskopfs Download PDF

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Publication number
EP2470372B1
EP2470372B1 EP20100795781 EP10795781A EP2470372B1 EP 2470372 B1 EP2470372 B1 EP 2470372B1 EP 20100795781 EP20100795781 EP 20100795781 EP 10795781 A EP10795781 A EP 10795781A EP 2470372 B1 EP2470372 B1 EP 2470372B1
Authority
EP
European Patent Office
Prior art keywords
layer
liquid
ejection head
manufacturing
liquid ejection
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP20100795781
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English (en)
French (fr)
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EP2470372A1 (de
Inventor
Tamaki Sato
Masafumi Morisue
Hirono Naito
Takumi Suzuki
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Canon Inc
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Canon Inc
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Publication date
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Publication of EP2470372A1 publication Critical patent/EP2470372A1/de
Application granted granted Critical
Publication of EP2470372B1 publication Critical patent/EP2470372B1/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/1637—Manufacturing processes molding
    • B41J2/1639—Manufacturing processes molding sacrificial molding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1601—Production of bubble jet print heads
    • B41J2/1603—Production of bubble jet print heads of the front shooter type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/1631—Manufacturing processes photolithography
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49401—Fluid pattern dispersing device making, e.g., ink jet

Definitions

  • the present invention relates to a method for processing a silicon substrate and a method for manufacturing a substrate for a liquid ejection head.
  • a liquid ejection head ejecting a liquid
  • an ink jet recording head applied to an ink jet recording method which performs recording by ejecting ink to a recording medium.
  • a liquid ejection head represented by the ink jet recording head includes flow paths, energy generating portions provided in the respective flow paths, and minute ejection ports for ejecting a liquid by energy generated in the energy generating portion.
  • a lithographic method using photosensitive materials is frequently employed in view of microfabrication and the like.
  • Patent Literature 1 a patterned layer of molds for flow paths is formed using a photosensitive material on a substrate having ejection energy generating portions, and subsequently, a covering layer formed into a flow path wall forming member is provided on the patterned layer. After openings used as ejection ports are formed in the covering layer on the patterned layer of molds for flow paths and at positions facing energy generating surfaces of the energy generating portions, the patterned layer is removed, so that rooms each functioning as a flow path are formed.
  • the covering layer is liable to be influenced by the shape of the patterned layer.
  • the thickness of the covering layer in the vicinity of the central portion of the patterned layer may be different from the thickness of the covering layer in the vicinity of the end portion of the patterned layer, and as a result, the distribution in thickness of the covering layer may be generated.
  • solvent coating of a liquid photosensitive resin is performed on a silicon wafer to form the covering layer, while a solvent of the photosensitive resin evaporates, the photosensitive resin spreads so as to get over the patterned layer.
  • the thickness of the covering layer located at a central side of the wafer is unfavorably different from the thickness of the covering layer located along an outer peripheral portion of the wafer.
  • the thickness of the covering layer on the patterned layer determines the length of a liquid path of an ejection port portion, when the variation in thickness of the covering layer occurs, the distance between the ejection port surface and the energy generating surface of the energy generating portion (element) may vary. Since this distance is a factor having a strong influence on the amount of a liquid to be ejected, when the above variation occurs, it becomes difficult to stably eject liquid droplets having uniform liquid volumes. This is a serious problem in the field of an ink jet recording method by the following reasons. Also US 2009/162797 A1 , US 2009/065474 A1 , and WO 2007/063690 A1 disclose methods which form ejection port openings in a layer which has been created by covering a patterned layer.
  • an ejected liquid droplet is required to be minimized, and the liquid ejection head is also increasingly required to satisfy the above requirement.
  • the present invention provides a method for manufacturing a liquid ejection head with good yield, the liquid ejection head being capable of suppressing variation in liquid volume of ejected liquid droplets and of stably and repeatedly ejecting liquid droplets having uniform liquid volumes.
  • a liquid ejection head which can suppress the variation in liquid volume of ejected liquid droplets and which can stably and repeatedly eject liquid droplets having uniform liquid volumes can be manufactured with good yield.
  • a liquid ejection head can be mounted on an apparatus such as a printer, a copying machine, a facsimile machine having a communication system, a word processor having a printer unit, and also an industrial recording apparatus integrally combined with various processing devices.
  • the liquid ejection head can also be used, for example, for biochip production, printing of electronic circuits, and spraying of chemicals.
  • Fig. 7 is a schematic perspective view showing one example of a liquid ejection head of the present invention.
  • the liquid ejection head of the present invention shown in Fig. 7 has a substrate 1 on which energy generating elements 2, each of which generates energy to eject a liquid such as ink, are formed with a predetermined pitch.
  • a supply port 3 which supplies a liquid is formed in the substrate 1 between two rows of the energy generating elements 2.
  • a flow-path wall member 4 which forms walls of the flow paths 6 communicating with the respective ejection ports 5 from the supply port 3 is integrally formed with an ejection port member in which the ejection ports 5 are provided.
  • Fig. 7 is a partially cutaway schematic perspective view of a liquid ejection head manufactured in the first embodiment.
  • Figs. 1A to 1J are schematic cross-sectional views showing the cross-section in each step taken along the line I-I of Fig. 7 perpendicular to the substrate 1.
  • a first layer 7 and a second layer 8 are evenly laminated to each other in this order on the substrate 1.
  • this substrate 1 provided with the above laminate thereon is prepared (first step).
  • the second layer 8 may be laminated on the first layer 7, or a laminate composed of the first layer 7 and the second layer 8, which is prepared beforehand in the form of a film, may be provided on the substrate 1 so that the first layer 7 is located at a substrate 1 side. Since being provided on the first layer 7 before molds for flow paths are formed therein, the second layer 8 is formed evenly on the surface of the substrate 1.
  • Molds 10 for flow paths are formed from the first layer 7, and ejection port forming members (A)9 are formed from the second layer 8. Since each of the molds 10 on the substrate 1 is finally removed, the first layer 7 can be formed from a material which can be easily removed by using a solvent. By the reason described above, the first layer 7 can be formed from a positive type photosensitive resin. Although through-holes used as the ejection ports are provided in the ejection port forming members (A)9, the through-holes can be formed by a photolithographic method to have minute dimensions with high positional accuracy. In addition, the ejection port forming members (A)9 are each required to have a mechanical strength as a structural member. By the reason described above, the second layer 8 can be formed from a negative type photosensitive resin.
  • the positive type photosensitive resin used for the first layer for example, a poly(methyl isopropenyl ketone) and a copolymer of methacrylic acid and a methacrylate may be mentioned as a suitable resin.
  • a poly(methyl isopropenyl ketone) and a copolymer of methacrylic acid and a methacrylate may be mentioned as a suitable resin.
  • the above compound can be easily removed by a commonly used solvent and that since the above compound has a simple composition, constituent components thereof have only a small influence on the second layer 8.
  • the negative type photosensitive resin used for the second layer 8 for example, a composition containing a resin having an epoxy group, an oxetane group, a vinyl group, or the like and a polymerization initiator corresponding to the above resin may be mentioned as a suitable composition.
  • a resin having the above functional group has high polymerization reactivity, the member (A)9 can be obtained to have a high mechanical strength.
  • the thickness of the first layer 7 and the thickness of the second layer 8 can be appropriately and separately determined.
  • the thickness of the first layer 7 is preferably set in a range of 3*10 -6 m to 15*10 -6 m
  • the thickness of the second layer 8 is preferably set in a range of 3*10 -6 m to 10*10 -6 m.
  • a photosensitive liquid repellent material may be provided on a predetermined surface of the second layer 8 for the purpose of imparting a liquid repellent function to the surface in which the ejection ports are provided.
  • the ejection port forming members (A)9 are formed from the second layer 8 (second step).
  • pattern exposure is performed on the second layer 8. This exposure is performed to form the ejection port forming members (A)9. Exposure is performed on the second layer 8 laminated on the first layer 7 having a flat upper surface through a mask 201, and exposed portions 21 are cured. Whenever necessary, curing may be promoted by heating.
  • the second layer 8 is developed, and non-exposed portions of the second layer 8 are removed, so that the ejection port forming members (A)9 are formed. In this case, as shown in Fig.
  • openings 23, parts of which are used as the ejection ports, are simultaneously formed.
  • the openings 23 can also be formed using an ejection port forming mask after the members (A)9 are formed by removing the non-exposed portions of the second layer 8.
  • the openings 23 can be formed at positions facing respective energy generating surfaces of the energy generating elements 2, the positional relationship is not limited to that described above.
  • the members (A)9 can be obtained from the second layer 8 to have substantially no variation in thickness. As shown in Fig. 1C , in view of simplification of the process, it is suitable that the openings 23 be simultaneously formed when the members (A)9 are formed.
  • the openings 23 partly used as the ejection ports can be formed in the members (A)9 by a dry etching method or the like after the third step, which will be described later, in which the molds for flow paths are obtained and before the fourth step in which a third layer is formed. Even in the case described above, since the members (A)9 are formed evenly in the second step, and the evenness thereof is maintained after the third step is performed, the lengths (liquid paths) (in the thickness direction of the member (A)9) of the obtained openings 23 are uniform within the substrate.
  • each of the members (A)9 surface of each member (A)9 opposite to the substrate 1 side
  • liquid repellence liquid repellence
  • an ink including a pigment or a dye is assumed as an ejection liquid, it is believed that liquid repellence at a water advance contact angle of approximately 80 degrees or more is sufficient.
  • a water advance contact angle of approximately 90 degrees or more is more preferable since the adhesion of the liquid to the member (A)9 can be further suppressed.
  • the mold 10 which has the shape of the flow path is formed from the first layer 7 (third step).
  • Fig. ID in order to form the mold for forming the flow path, exposure is performed on the first layer 7 through a mask 202.
  • the molecular weight of a resin in portions 22 processed by the exposure is decreased, and hence the exposed resin is likely to be dissolved in a developing solution.
  • exposure is performed on portions (exposed portions 22) of the first layer 7 located outside the members (A)9.
  • Fig. 1E development is performed on the first layer 7 using a suitable developing solution to remove the exposed portions 22, so that the mold 10 is formed. At least two molds 10 can be obtained from the first layer 7.
  • a third layer 11 in close contact with the molds 10 and the members (A)9 is provided to have a height (thickness) larger than that of an upper surface 24 of the mold 10 (fourth step).
  • the third layer 11 is formed to have a thickness larger than the thickness of the mold 10 from the upper surface of the substrate 1, to cover the molds 10, and to come into close contact with the members (A)9.
  • the third layer 11 is formed to have a thickness of more than 3*10 -6 m from the energy generating surface.
  • the thickness of the third layer 11 is preferably set to 40* 10 -6 m or less.
  • the upper surface position thereof may be higher (larger) than, may be equivalent to, or may be lower (smaller) than the position of an upper surface 13 of the member (A)9.
  • the thickness of the third layer 11 may be formed so as to be small as compared to the upper surface 13 of the member (A)9.
  • the third layer 11 is partially filled in the openings 23 used as the ejection ports.
  • the third layer 11 can be formed of a negative type photosensitive resin having the same composition as that of the second layer 8, and suitably, a compound contained in the third layer 11 is the same as that contained in the second layer 8.
  • the composition ratio is not necessarily the same.
  • a portion 26 located in the opening 23 used as the ejection port and an upper portion 27 located on the portion 26, which are parts of the third layer 11, must be removed, the portion 26 and the upper portion 27 are shaded by the mask 203.
  • portions onto which the exposure is not performed are removed, for example, by a liquid development method.
  • a suitable solvent such as xylene, may be used according to the composition of the negative type photosensitive resin.
  • the non-exposed portions of the third layer 11, that is, the portion inside the opening 23 used as the ejection port and the portion thereon, are removed.
  • the supply port 3 is formed in the substrate 1 by dry etching or the like. Accordingly, the mold 10 communicates with the outside.
  • the mold 10 for forming the flow path is dissolved by a suitable solvent, and the liquid flow path 6 is formed so as to communicate with the ejection ports 5 (fifth step).
  • the flow-path wall member 4 has a wall surface 12 adjacent to the surface in which the ejection ports 5 are formed.
  • the distance between the wall surface 12 and the ejection port 5 is set so that an ejection liquid can form a meniscus in the ejection port 5, that is, at a substrate side apart from an opening surface 14.
  • the distance from the wall surface 12 to the edge of the ejection port 5 is preferably 80* 10 -6 m or more.
  • the members (A)9 and the molds 10 are evenly formed, and hence, within the substrate, a distance D from the energy generating surface of the substrate 1 to the ejection port 5 becomes uniform. Hence, the amounts of liquid ejected from a plurality of ejection ports can be made constant.
  • a liquid repellent function may be imparted to the opening surface 14 of the ejection port 5.
  • a second embodiment of the present invention will be described with reference to Figs. 3A to 3E , 4A , 4B , and 5 .
  • a liquid repellent treatment is performed on the surface of the ejection port.
  • Figs. 3A to 3E are cross-sectional views showing the cross-section in each step as in the case shown in Figs. 1A to 1J
  • Figs. 4A , 4B , and 5 are cross-sectional views each illustrating the state in the manufacturing step. The position of the cutting plane is the same as that of Figs. 1A to 1J .
  • Steps from the start to the step (first step) shown in Fig. 1A are performed in a manner similar to that in the first embodiment. Subsequently, the following is performed in a step (second step) of forming the members (A)9.
  • a liquid repellent material 15 for imparting liquid repellence is provided to the upper surface of the second layer 8.
  • the liquid repellent material 15 may be allowed to partially or entirely permeate into the second layer 8.
  • a liquid to be ejected is an aqueous or an oily ink
  • sufficient repellence may be obtained by a liquid repellent material having a thickness of 2*10 -6 m in a direction perpendicular to the substrate 1 to which liquid repellence is imparted.
  • the liquid repellent material 15 is evenly laminated on the substrate.
  • a photosensitive fluorine-containing epoxy resin film or a composition containing a condensate of a fluorine-containing silane and a silane containing a polymerization group may be used for the liquid repellent material 15.
  • the liquid repellent material 15 and the second layer 8 can be collectively patterned by photolithography.
  • a shade portion 16a is provided in an aperture 50 of the mask 16 so that a portion of the second layer 8 corresponding to the aperture 50 is exposed and a portion of the liquid repellent material 15 corresponding to the shade portion 16a is not exposed.
  • the width of the shade portion 16a is determined in consideration of the resolutions of the second layer 8 and the liquid repellent material 15.
  • a liquid repellant portion 17 having liquid repellence is provided on the upper surface of the member (A)9 around the opening 23 which is used as the ejection port.
  • liquid repellant material provided on a region other than that around the opening 23 is removed, liquid repellence is not imparted to the above region.
  • through-holes 18 may be provided in the member (A)9 as shown in Fig. 4A .
  • the third layer 11 provided on the upper surface of the member (A)9 is partially filled in the hole 18, and the inner wall of the hole 18 and the third layer 11 are brought into contact with each other.
  • the bonding strength between the member (A)9 and the third layer 11 can be increased.
  • grooves 19 are formed in the member (A)9 as shown in Fig. 4B , and the inner wall of the groove 19 and the third layer 11 can be brought into contact with each other.
  • the mold 10 is formed in a manner similar to that of the method described with reference to Fig. 1E (third step), and subsequently, as shown in Fig. 3D , the third layer 11 is formed on the upper surface of the member (A)9 (fourth step).
  • the third layer 11 may be repelled on the liquid repellant portion 17 of the member (A)9, the third layer 11 is not repelled on the upper surface of the member (A)9 on which the liquid repel portion 17 is not provided and is brought into close contact with the upper surface of the member (A)9.
  • the third layer is brought into close contact therewith.
  • the mold 10 is removed to form the flow path 6 (fifth step), and as shown in Fig. 3E , the liquid ejection head is obtained.
  • liquid repellence is imparted to the opening surface 14 at which the ejection port 5 of the member (A)9 is open, an ejection liquid 30 filled in the flow path does not stay on the opening surface 14 (see Fig. 5 ) but can reliably form a meniscus at a position approximately equivalent to that of the ejection port 5.
  • liquid repellence is imparted to the opening surface 14, even when an ejected liquid partially floats in the form of mist and adheres on the opening surface 14, the mist is not fixed to the opening surface 14 and can be easily removed, for example, by suction of a suction mechanism equipped in an ejection apparatus.
  • FIGS. 2A to 2G are cross-sectional views showing the cross-section in each step as in the case shown in Figs. 1A to 1J , and the position of the cutting plane is the same as that of Figs. 1A to 1J .
  • the first layer 7 of a positive type photosensitive resin is exposed using the members (A)9 as a shade mask.
  • the member (A)9 can absorb light having a wavelength in a range of 200 nm to 300 nm.
  • the sensitive wavelength of many positive type photosensitive resins is 220 nm to 300 nm; hence, the first layer 7 is exposed by light having a wavelength of 220 nm to 300 nm by using the members (A)9 as a shade mask, the resin in the exposed first layer 7 can be decomposed.
  • the molds 10 for flow paths can be obtained. Since the shape of the mold 10 for the flow path is formed in accordance with the shape of the member (A)9 in a direction parallel to the surface of the substrate 1, the outline of the member (A)9 must be formed beforehand so as to correspond to the shape of the flow path.
  • the member (A)9 which is in contact with the first layer 7 is used as a shade mask, the alignment accuracy therebetween can be improved. In addition, the first layer is suppressed from being exposed by light diffracted by the shade mask.
  • the third layer 11 is provided so that the thickness thereof is higher than the upper surface of the mold 10 (fourth step).
  • Fig. 2D exposure is performed on the third layer 11 through the mask 203, and the exposed portions 25 of the third layer 11 are cured.
  • Fig. 2E non-exposed portions are removed, and the openings 23 are formed.
  • Fig. 2F the supply port 3 is formed in the substrate 1.
  • the mold 10 is removed, and the flow path 6 and the ejection ports 5 are formed, so that the liquid ejection head in the state shown in Fig. 2G is obtained (fifth step).
  • Example 1 With reference to Figs. 1A to 1J , Example 1 will be described assuming that the substrate 1 is a part of a substrate before it is cut into small pieces.
  • the substrate 1 (6-inch wafer) provided with the first layer 7 and the second layer 8 was prepared ( Fig. 1A ).
  • ODUR-1010 manufactured by Tokyo Ohka Kogyo Co., Ltd.
  • a spin coating method drying was performed at 120 degrees centigrade, so that the first layer 7 was formed.
  • the average thickness of the first layer 7 after its formation was 7*10 -6 m, and the standard deviation of the thickness of the first layer 7 within the substrate 1 (6-inch wafer) was 0.1*10 -6 m or less (350 positions in the 6-inch wafer were measured).
  • the second layer 8 was exposed using a mask aligner MPA-600 Super (product name) manufactured by CANON KABUSHIKI KAISHA ( Fig. 1B ).
  • the exposure dose was 1 J/cm 2
  • a mixed liquid of methyl isobutyl ketone/xylene at a ratio of 2/3 was used as a developing solution
  • xylene was used as a rinse agent after development.
  • the first layer 7 was irradiated at 10 J/cm 2 with deep-UV light (wavelength of 220 nm to 400 nm) using a mask aligner UX-3000SC (product name) manufactured by Ushio, Inc. ( Fig. 1D ).
  • the first layer 7 was rinsed with isopropyl alcohol, and the exposed portions of the first layer 7 were removed, so that the molds 10 for flow paths were formed ( Fig. 1E ).
  • the composition shown in Table 1 was applied on the members (A)9 and the molds 10, so that the third layer 11 was formed ( Fig. 1F ).
  • the third layer 11 was formed so that the thickness from the surface of the substrate 1 to the upper surface of a part of the third layer located above the member (A)9 was 18*10 -6 m.
  • the molds 10 on the substrate 1 were dissolved by methyl lactate and were removed, so that the ejection ports 5 each having a diameter of 12*10 -6 m were formed ( Fig. 1J ).
  • the average distance D was 12*10 -6 m, and the standard deviation thereof was 0.25*10 -6 m.
  • 350 ejection ports in the wafer were evenly selected from the center to the end of the wafer, and the distance D was obtained from each ejection port by measurement.
  • FIGS. 6A and 6B are cross-sectional views each illustrating the state in the step of manufacturing a liquid ejection head according to this example of the present invention.
  • the position of the cutting plane is the same as that of Figs. 1A to 1J .
  • Example 2 from Example 1 Different points of Example 2 from Example 1 were as follows.
  • the thickness of the second layer 8 from the upper surface of the first layer 7 was set to 10* 10 -6 m, and the third layer 11 was formed so that the height of the upper surface of a portion thereof provided on the first layer 7 was set to 5*10 -6 m from the upper surface of the first layer 7.
  • the third layer 11 was provided so that the upper surface thereof was located lower than the upper surface of the member (A)9.
  • the others points of this example were performed in a manner similar to that in Example 1.
  • Fig. 6B shows the liquid ejection head formed as described above.
  • the ejection port 5 was provided at a position higher than the upper surface of an outer wall portion 4a of the flow-path wall member 4 based on the substrate.
  • the average distance D was 17*10 -6 m, and the standard deviation of the distance D was 0.25*10 -6 m.
  • 350 ejection ports in the wafer (6-inch wafer) were evenly selected from the center to the end of the wafer, and the distance D of each ejection port was measured.
  • Figs. 8A to 8F are cross-sectional views of steps of forming a liquid ejection head according to the comparative example.
  • ODUR-1010 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied on a silicon substrate 101 (6-inch wafer) provided with energy generating elements 102, drying was performed, so that a layer 103 of a positive type photosensitive resin having a thickness of 7*10 -6 m was formed on the substrate 101 ( Fig. 8A ).
  • Example 1 the composition shown in Table 1 of Example 1 was applied on the mold 104 using a spin coating method, followed by performing drying at 90 degrees centigrade for 3 minutes, so that a covering layer 105 was formed.
  • the covering layer 105 was formed so that a portion thereof provided on the upper surface of the mold 104 had a thickness of 7*10 -6 m ( Fig. 8C ).
  • Non-exposed portions of the covering layer 105 were removed by development, so that a member 111 forming walls of the flow paths and ejection ports 107 each having a diameter of 12*10 -6 m were formed ( Fig. 8E ).
  • the 6-inch wafer was cut by a dicing saw, and one liquid ejection head unit was separated.
  • the average value of a distance h from the energy generating surface of the energy generating element 102 of the substrate 101 to the ejection port 107 was 12*10 -6 m.
  • the standard deviation of the distance h was 0.6*10 -6 m.
  • 350 ejection ports in the wafer were evenly selected from the center to the end of the wafer, and the distance h was obtained from each ejection port by measurement.
  • Test recording was performed using the liquid ejection heads of Examples 1 and 2 and Comparative Example 1. The recording was performed using a plurality of liquid ejection heads cut out from the same 6-inch wafer. In addition, a liquid ink containing pure water/diethylene glycol/isopropyl alcohol/lithium acetate/black dye food black 2 at a ratio of 79.4/15/3/0.1/2.5 was used, and the recording was performed at an ejection volume Vd of 1 picoliter and an ejection frequency f of 15 kHz.

Claims (13)

  1. Verfahren zum Herstellen eines Flüssigkeitsausstoßkopfes, der eine Ausstoßöffnung (5) zum Ausstoßen einer Flüssigkeit und einen mit der Ausstoßöffnung in Verbindung stehenden Strömungsweg (6) enthält, wobei das Verfahren in der angegebenen Reihenfolge umfasst:
    einen ersten Schritt des Vorbereitens eines Substrats (1), auf dem eine erste Schicht (7) und eine zweite Schicht (8) in dieser Reihenfolge eben laminiert sind;
    einen zweiten Schritt des Erzeugens eines Elements (9) zum Erzeugen der Ausstoßöffnung aus der zweiten Schicht;
    einen dritten Schritt des Erzeugens einer Form (10) zum Erzeugen des Strömungswegs aus der ersten Schicht;
    einen vierten Schritt des Bereitstellens einer dritten Schicht (11), sodass die Form bedeckt ist und sodass ein naher Kontakt mit dem Element besteht; und
    einen fünften Schritt des Entfernens der Form, um den Strömungsweg zu erzeugen,
    dadurch gekennzeichnet, dass
    im zweiten Schritt eine als die Ausstoßöffnung verwendete Ausnehmung (23) im Element erzeugt wird.
  2. Verfahren zum Herstellen eines Flüssigkeitsausstoßkopfes nach Anspruch 1, wobei der erste Schritt einen Teilschritt des Bereitstellens der ersten Schicht, beinhaltend ein unbelichtetes photosensitives Harz vom Positiv-Typ, auf dem Substrat und einen Teilschritt des Bereitstellens der zweiten Schicht auf der ersten Schicht enthält, und wobei nach dem zweiten Schritt Belichtung der ersten Schicht durchgeführt wird, um die Form zu Erzeugen.
  3. Verfahren zum Herstellen eines Flüssigkeitsausstoßkopfes nach Anspruch 1 oder 2, wobei die dritte Schicht so bereitgestellt wird, dass sie eine Höhe entsprechend oder niedriger als eine obere Fläche (13) des Elements aufweist.
  4. Verfahren zum Herstellen eines Flüssigkeitsausstoßkopfes nach Anspruch 1, wobei, bevor der vierte Schritt durchgeführt wird, einem Abschnitt in der Peripherie der Ausnehmung des Elements die Fähigkeit verliehen wird, Flüssigkeit abzuweisen.
  5. Verfahren zum Herstellen eines Flüssigkeitsausstoßkopfes nach einem der Ansprüche 1 bis 3, wobei, bevor der vierte Schritt durchgeführt wird, ein flüssigkeitsweisender Abschnitt (17) und ein nicht-flüssigkeitsabweisender Abschnitt auf einer dem Substrat gegenüberliegenden Oberfläche des Elements bereitgestellt werden.
  6. Verfahren zum Herstellen eines Flüssigkeitsausstoßkopfes nach Anspruch 5, wobei der flüssigkeitsabweisende Abschnitt ein Abschnitt in der Peripherie der Ausnehmung des Elements ist und das Element an dem nicht-flüssigkeitsabweisenden Abschnitt mit der dritten Schicht in Kontakt steht.
  7. Verfahren zum Herstellen eines Flüssigkeitsausstoßkopfes nach Anspruch 5 oder 6, wobei im zweiten Schritt ein Material (15), das die Fähigkeit verleiht, Flüssigkeit abzuweisen, auf der zweiten Schicht bereitgestellt wird, die Fähigkeit, Flüssigkeit abzuweisen, einem Abschnitt (17) in der Peripherie der Ausnehmung durch das Material verliehen wird, und das auf einem von dem in der Peripherie der Ausnehmung verschiedenen Abschnitt bereitgestellte Material entfernt wird.
  8. Verfahren zum Herstellen eines Flüssigkeitsausstoßkopfes nach Anspruch 7, wobei im zweiten Schritt, wenn das Material entfernt wird, ein Abschnitt (18, 19) der zweiten Schicht, der sich unter dem entfernten Material befindet, gleichzeitig entfernt wird.
  9. Verfahren zum Herstellen eines Flüssigkeitsausstoßkopfes nach einem der Ansprüche 1 bis 8, wobei die zweite Schicht ein photosensitives Harz vom Negativ-Typ enthält.
  10. Verfahren zum Herstellen eines Flüssigkeitsausstoßkopfes nach einem der Ansprüche 1 bis 9, wobei die zweite Schicht und die dritte Schicht photosensitive Harze vom Negativ-Typ enthalten, welche die gleiche Zusammensetzung aufweisen.
  11. Verfahren zum Herstellen eines Flüssigkeitsausstoßkopfes nach einem der Ansprüche 1 bis 10, wobei im zweiten Schritt des Erzeugens des Elements die Form des Elements erzeugt wird, um der Form des Strömungswegs zu entsprechen, und unter Verwendung des Elements als Maske die Form erzeugt wird durch Entfernen eines Abschnitts der ersten Schicht, auf dem das Element nicht laminiert ist.
  12. Verfahren zum Herstellen eines Flüssigkeitsausstoßkopfes nach einem der Ansprüche 1 bis 11, wobei die erste Schicht ein photosensitives Harz vom Positiv-Typ enthält, und, nach Belichtung der ersten Schicht unter Verwendung des Elements als Maske, die Form durch Entfernen des belichteten Abschnitts erzeugt wird.
  13. Verfahren zum Herstellen eines Flüssigkeitsausstoßkopfes nach Anspruch 1, wobei, nach Durchführung des fünften Schritts, einem Abschnitt (17) in der Peripherie der Ausnehmung des Elements die Fähigkeit verliehen wird, Flüssigkeit abzuweisen.
EP20100795781 2009-11-11 2010-11-02 Verfahren zur herstellung eines flüssigkeitsausstosskopfs Not-in-force EP2470372B1 (de)

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JP2009258192A JP5279686B2 (ja) 2009-11-11 2009-11-11 液体吐出ヘッドの製造方法
PCT/JP2010/006474 WO2011058719A1 (en) 2009-11-11 2010-11-02 Method for manufacturing liquid ejection head

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6000715B2 (ja) * 2011-09-29 2016-10-05 キヤノン株式会社 液体吐出ヘッドの製造方法
JP2014162038A (ja) * 2013-02-22 2014-09-08 Seiko Epson Corp 流路ユニット、液体噴射ヘッド、液体噴射装置、流路ユニットの製造方法
WO2014133561A1 (en) 2013-02-28 2014-09-04 Hewlett-Packard Development Company, L.P. Molding a fluid flow structure
US9656469B2 (en) 2013-02-28 2017-05-23 Hewlett-Packard Development Company, L.P. Molded fluid flow structure with saw cut channel
CN107901609B (zh) 2013-02-28 2020-08-28 惠普发展公司，有限责任合伙企业 流体流动结构和打印头
US10821729B2 (en) 2013-02-28 2020-11-03 Hewlett-Packard Development Company, L.P. Transfer molded fluid flow structure
US9731509B2 (en) 2013-02-28 2017-08-15 Hewlett-Packard Development Company, L.P. Fluid structure with compression molded fluid channel
US9724920B2 (en) 2013-03-20 2017-08-08 Hewlett-Packard Development Company, L.P. Molded die slivers with exposed front and back surfaces
KR102030735B1 (ko) 2018-01-26 2019-10-11 광주과학기술원 분광장치 및 분광방법

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3143307B2 (ja) * 1993-02-03 2001-03-07 キヤノン株式会社 インクジェット記録ヘッドの製造方法
JPH08174833A (ja) * 1994-12-21 1996-07-09 Canon Inc インクジェット記録装置の記録ヘッドおよびその基板端面への酸化皮膜形成方法
US6461798B1 (en) * 1995-03-31 2002-10-08 Canon Kabushiki Kaisha Process for the production of an ink jet head
JP3343875B2 (ja) * 1995-06-30 2002-11-11 キヤノン株式会社 インクジェットヘッドの製造方法
US6137510A (en) * 1996-11-15 2000-10-24 Canon Kabushiki Kaisha Ink jet head
US7090325B2 (en) * 2001-09-06 2006-08-15 Ricoh Company, Ltd. Liquid drop discharge head and manufacture method thereof, micro device ink-jet head ink cartridge and ink-jet printing device
US6986982B2 (en) * 2002-02-20 2006-01-17 Canon Kabushiki Kaisha Resist material and method of manufacturing inkjet recording head using the same
US6869541B2 (en) * 2002-02-21 2005-03-22 Canon Kabushiki Kaisha Epoxy resin composition, surface treating method, ink-jet recording head, and ink-jet recording apparatus
JP2005074747A (ja) * 2003-08-29 2005-03-24 Canon Inc インクジェットヘッドの製造方法およびインクジェットヘッド
US7322104B2 (en) * 2004-06-25 2008-01-29 Canon Kabushiki Kaisha Method for producing an ink jet head
JP4761498B2 (ja) * 2004-06-28 2011-08-31 キヤノン株式会社 感光性樹脂組成物、ならびにこれを用いた段差パターンの製造方法及びインクジェットヘッドの製造方法
JP4484774B2 (ja) 2004-06-28 2010-06-16 キヤノン株式会社 液体吐出ヘッドの製造方法
DE602005015974D1 (de) * 2004-06-28 2009-09-24 Canon Kk Kopfs und unter verwendung dieses verfahrens erhaltener flüssigkeitsabgabekopf
JP4533256B2 (ja) * 2004-06-28 2010-09-01 キヤノン株式会社 微細構造体の製造方法および液体吐出ヘッドの製造方法
JP2006069009A (ja) * 2004-09-01 2006-03-16 Canon Inc インクジェットヘッドの製造方法
JP4614383B2 (ja) * 2004-12-09 2011-01-19 キヤノン株式会社 インクジェット記録ヘッドの製造方法、及びインクジェット記録ヘッド
KR100657334B1 (ko) * 2005-09-13 2006-12-14 삼성전자주식회사 잉크젯 프린터 헤드의 제조 방법 및 상기 방법에 의하여제조된 잉크젯 프린터 헤드
EP1957282B1 (de) * 2005-12-02 2013-04-10 Canon Kabushiki Kaisha Verfahren zur herstellung eines flüssigkeitsausstosskopfs
JP2008046584A (ja) * 2006-07-19 2008-02-28 Fujifilm Corp カラーフィルタの製造方法
US7909428B2 (en) * 2006-07-28 2011-03-22 Hewlett-Packard Development Company, L.P. Fluid ejection devices and methods of fabrication
JP4480182B2 (ja) * 2007-09-06 2010-06-16 キヤノン株式会社 インクジェット記録ヘッド用基板及びインクジェット記録ヘッドの製造方法
KR20090030111A (ko) * 2007-09-19 2009-03-24 삼성전자주식회사 잉크젯 프린터 헤드의 제조 방법 및 상기 방법에 의하여제조된 잉크젯 프린터 헤드
US20090162797A1 (en) * 2007-12-19 2009-06-25 Canon Kabushiki Kaisha Method of manufacturing liquid ejection head
KR101452705B1 (ko) * 2008-01-10 2014-10-24 삼성전자주식회사 잉크젯 프린터 헤드의 제조 방법 및 상기 방법에 의하여제조된 잉크젯 프린터 헤드
JP5094519B2 (ja) 2008-04-14 2012-12-12 オリンパス株式会社 走査型レーザ顕微鏡
KR20090117010A (ko) * 2008-05-08 2009-11-12 삼성전자주식회사 잉크젯 프린터 헤드의 제조 방법 및 상기 방법에 의하여제조된 잉크젯 프린터 헤드
JP5312202B2 (ja) * 2008-06-20 2013-10-09 キヤノン株式会社 液体吐出ヘッド及びその製造方法
US8262199B2 (en) * 2008-09-30 2012-09-11 Fujifilm Corporation Droplet jetting head, method of manufacturing droplet jetting head, and droplet jetting apparatus equipped with droplet jetting head
US8844123B2 (en) * 2009-12-03 2014-09-30 Chin-Chi Yang Method of manufacturing a hollow surface mount type electronic component

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KR101327674B1 (ko) 2013-11-08
US20120222308A1 (en) 2012-09-06
EP2470372A1 (de) 2012-07-04
KR20120079171A (ko) 2012-07-11
JP5279686B2 (ja) 2013-09-04
WO2011058719A1 (en) 2011-05-19
CN102596575B (zh) 2014-08-27
JP2011102001A (ja) 2011-05-26

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